Metallized azo dyes from 2-aminopyridine-1-oxide



Patented Aug. 13, 1963 3,100,766 METALLIZED AZO DYES FROM 2-AMlN0- PYRIDINE-l-OXIDE Charles E. Lewis, Somerville, N.J., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed May 19, 1961, Ser. No. 111,134

reacting a 2-(R-azo)rnonazine-N-'oxide, as above defined with a salt of a metal having an atomic number greater than 23 and less than 30.

The metallization reaction is preferably conducted by heating the N-oxide with lirom about 0.5 to about 2 moles of the metal salt in an organic solvent such as dimethylform-amide, formamide, pyridine, aniline or an alcohol.

3 Claims- Reaction temperatures are from about 75-150 C. preferabl =w'thin the ran t about 90 to about 140 C. This invention relates to new metallized azo comy l ge [of Metallization Will 0 to substantial com letion in a eriod Pounds which are as ,dyestufis, especially for fibers of less than about 3 or 4 hours. After metallizatio ii, the such as wool and silk; the linear polyamides, e.g., nylon; metal complex is Team-1y separated from the reaction and the Pmtemaceous fibers PTePared from natural mixture by drowning in water and filtration of the resultteins as disclosed in Man-Man Textile Encyclopedia (pp. ing precipitate. 109411). Among the metal salts useful for the purpose of this Meta1hZ,at1u 9 i dyestuffs for the PHI-PO56 invention may be mentioned salts of inorganic acids such lncreasmg hght Stabfllty has been knownas sulfuric, nitric and hydrochloric acids; and salts of ous attempts have been made to utilize this principle for organic acids Suoh as formic, acetic and lactic acids increasing the stability of dyestuffs from azopyridine-N- Among the N oxides useful the purposes this oxides and azoquinoline-N-oxides. However, such N- venfion oxides did not lend themselves to successful metalliza- (1) 2 (2:hydroxy 5 Y phenylazol) 9 Thus" metal complexes could not fm f oxides such as the derivatives wherein Y is hydrogen or either 2-(p-dlmethylannnophenylazo)-pyr1dme-N-ox1de, methyl. 4(4-hydroxy-1-naphthylazo)pyridine-Dioxide or 4-(4- (2) -5,6,7 r 8-Z-1-napl1thy1 Z P h Q P Q dine-N-oxides, wherein Z is a hydrogen, 6-su1famyl, 7-

It 1s an ObJCCt of this mvention to provide metallized chloro 6dmethyl. derivatives or arylazo monazine-N-oxides which are use- (3) slglmaphthylazo) pyridine m1 dyeing mtwgeilous N-0Xides wherein Z is hydrogen, 6-sulfo, 7-bromo or 5- It is a further ob ect of this invention to provide n1- methyl. trogenons libers dyed with metallized derivatives of aryl- (4) 5 Y phenylazo) quinolinc azomonazme'Noxlfies clas? helemafter desmbed' oxides such as the derivatives wherein Y is hydrogen or In accorclllance with this mventgon 1t has 1 :l;1een2foung methyL that metals aving an atomic nunr er greater an 3 an (5) 2 (2 hydroXy 56,7 0r 8 Z 1 naphthy1am) quino less than N1 i Cu) l-ine-N-oxides wherein Z is hydrogen, 7-sulfamyl, 6-bromo plexes Wlllll 2-(R-az0)-monaz1ne-N-ox1des wherein the or 5 methy1. and monazineradical has less than three six-membered rings (6) 2 (iamhw 5 7 8.Z-1 1 thylazo)-qnino- Pyndyl and qumolyl) and R a Tadlcal of the line-N-oxides wherein Z is a hydrogen, 6-sulfo, 7-bromo group or S-methyl.

011 Where the desired N-oxide starting material is not known, it may be prepared by diazotizing Z-amino-py-ri- Q dine-N-oxide or Z-amino-qu-inoline-N-oxide, as the case I may be, coupling with the coupling agent corresponding Y to the R radical shown on the azo linkage of the start- OH 45 ing material. Diazotization, coupling agents, coupling l conditions useful for this purpose are conventional in the art.

The metallized azo dyes of the present invention have affinity for wool, silk, linear polyamide and artificial proteinaceous fibers, which they dye level, deep reddish Z shades. They are generally applied by the so called neutral dyeing method which employs ammonium aceand tate or acetic acid in small amounts to give the dyeing N Hi bath a weakly acidic pH. They exhaust well and give level shades.

Q The following examples are presented to more fully illustrate the present invention. Parts are by Weight unless otherwise noted.

Z Example 1 wherein Y is hydrogen or lower alkyl; and Z is hydro- (A) OH gen, sulfamyl, sulfo, halo (e.g. chloro, bromo and iodo), I and alkyl (e.g., lower alkyl such as methyl, ethyl and propyl), which complexes dye nitrogenous fibers level, l deep shades when applied by conventional neutral dyeing 0 methods. I

The metallized dyes of this invention are prepared by g,

.3 4 11.0 parts of 2-arninopyridine-1-oxide are dissolved in until uniform, filtered, Washed with cold Water and dried 160 parts of 7.5% hydrochloric acid and cooled to 0 C. at 50 C. It is then recrystallized from 50% ethanol.

6.9 parts of sodium nitrite dissolved in 13.4 parts of Water (B) Copperization of the prodzwts of part A.-1.32

are added all at once and stirred at 0 C. for 15 min. until parts of the product of part A, 1.0 part of cupric acetate diazotization is complete. (An orange color develops.) 5 monohydrateslurried in 25 parts by volume of formamide 23.7 parts of real 2-naphthol-6-sulfonamide are disare heated three hours at 90-100 C. The Whole is then r i ll Wolltl llllllltd With'anfitualvolumcotwatcr and filtered.

l r l 5 sulfo, halo and lower alkyl; and vthe metal has an atomic number greater than 23 and less than 30.

2. The chromium complex of 2-(2-hydr0Xy-5-sulfamyll-naphthylazo pyridine-N-oxide.

3. The copper complex of 2-(2-l1yd1 oXy-1-naphthylazo) -pyridine-N-ox-icle.

References Cited in the file of this patent UNITED STATES PATENTS 1,827,680 Tisza et a1. Oct. 13, 1931 6 2,903,324 Hirsbrunner Sept. 8, 1959 2,929,809 Menzi et al Mar. 22, 1960 2,957,862 Riat et a1. Oct. 25, 1960 2,987,368 Bene June 6, 1961 1955, pp. 1508-1518. (Available in Scientific; Li-

brary. 

1. A METAL COMPLEX OF A 2-(R-AZO) -MONAZINE-N-OXIDEWHEREIN THE MONAZINE RADICAL CONTAINS LESS THAN THREE SIX-MEMBERED RINGS AND R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF 